Abstract
The redox properties of heterogenized RhI, RhII, and RhIII complexes with different, particularly organophosphorus, ligands were studied by cyclic voltammetry (CVA). The support is a carbon-paste electrode based on a fibrous-carbon material and activated carbon. The electrochemical reduction of RhIII produces Rh metal, which further catalyzes hydrogen evolution. After the reduction of water-soluble binuclear RhII complexes, the CVA curves exhibit peaks of electrocatalytic hydrogen evolution and irreversible RhI→RhII oxidation. The RhII complexes with organophosphorus ligands are characterized only by the peak of RhI→RhII oxidation. After reduction, the RhI complexes behave as a pseudo-reverse Rh0/RhI pair. The electron-donating properties of the ligand determine the reversibility of the system. The degree of structurization of the carbon matrix and the presence of phosphorus(v) atoms in it affect the electrochemical activity of the RhII and RhI complexes.
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